Heteromorphic Lysine Feed Granules

ABSTRACT

A heteromorphic granule comprising lysine free base and a lysine salt is disclosed. A fertilizer composition is set forth having cores containing an acid salt of a basic amino acid and effective amounts of first and second layer coatings coated sequentially to the surface of each core. A method for using the heteromorphic granule as a fertilizer and/or an animal feed is provided.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Patent Application Ser. No60/995,561 filed Sep. 27, 2007. The entire contents of U.S. PatentApplication Ser. No. 60/995,561 is incorporated by reference into thisapplication

FIELD OF THE INVENTION

This disclosure is directed towards free flowing animal feed supplementscontaining mixtures of various amino acids or those of freebase aminoacids intermixed with salts of amino acids.

BACKGROUND

The following background material includes information that may beuseful in understanding the present teaching. It is not an admissionthat any of the information provided herein is prior art, or material,to the presently described or claimed disclosures, or that anypublication or document that is specifically or implicitly referenced isprior art.

L-lysine is an essential amino acid that is supplied as a feedsupplement for both monogastric and ruminant animals lysine feedsupplements are commercially supplied in essentially three forms—asdried granules of lysine-HCl salt (often called merely lysine HCL), as adried broth from a fermenter from which the lysine was made by bacterialfermentation (often referred to as lysine sulfate because thepredominant form of the lysine from a dried broth is as a sulfate salt)and finally as free lysine that is supplied as liquid solution to besprayed onto animal feed as a supplement (often called lysine freebase).There are minor variations in some compositions of these three forms oflysine feed. For example, lysine HCl granules may include minor amountsof anti-caking agents to improve flow properties, dried lysine sulfatemay or may not include the bacterial cell mass from the fermentationbroth, and lysine freebase may be supplied in different liquidconcentrations.

Each of the three forms of commercially available lysine feedsupplements have advantages and disadvantages. Some advantages of lysineHCl are that the dried granules are relatively speaking, pure,inexpensive to ship, easy to control in terms of productionspecifications, and have low hygroscopic character. The majordisadvantages are that it is costly to make because it requirespurification and crystallization of lysine from a fermentation broth,and only 80% of the weight of the product is lysine—the remainder beingthe HCl. The major advantage of lysine sulfate is that it is simplest tomake, however, its disadvantages are that the product has variablecomposition because it is simply a dried fermentation broth, and for thesame reason is relatively impure, with typically no more than 50% of thedry weight of the product being lysine. The major advantages of lysinefreebase are that the lysine product in solution high purity, and theease of shipping and handling a liquid. The major disadvantages oflysine freebase is that because it is provided as a solution, shippingcosts on a lysine content basis are higher than for the other dryproducts, and that dedicated mixing equipment is needed to dispense theproduct onto animal feed.

lysine may also be used in the agricultural industry as a fertilizer.The nitrogen content of lysine is sufficient for practical use asfertilizer, which has the advantages of being organic, biodegradable anda source of nutrition for soil microbes. lysine alone, however, lacksother mineral ingredients such as potassium and phosphate that are oftenadded to a fertilizer. The same advantages and disadvantages of thethree forms of lysine mentioned above apply equally when the product isused as a fertilizer.

Although it would seem desirable to sell lysine freebase as a driedproduct to lower shipping and production costs, from a commercialstandpoint such a product is not desirable because lysine freebase ismuch more hygroscopic than lysine HCl or lysine sulfate, causing theproduct to cake, swell and loose the free flowing properties that make adried product easy to manage and dispense. There is therefore, a need inthe art to provide a dried lysine feed product that has at least some ofthe advantages of lysine freebase but without the disadvantages thatmake such a product undesirable.

The present disclosure addresses this need and others that will beapparent from the disclosure that follows.

SUMMARY

Described herein are various embodiments of heteromorphic lysinegranules and mixtures. These embodiments are a combination of driedlysine freebase blended with—or agglomerated into a layered structurewith—various amounts of lysine HCl, salt particles, other amino acids orother crude sources of lysine. These heteromorphic granules and mixturesoffer many of the advantages of lysine HCl in terms of ease of use andlow hygroscopic character, while providing at least a portion of theadvantages of lysine freebase in terms of purity and ease of production.The teachings of this disclosure are concerned with new lysine productsthat incorporate dried lysine freebase. Currently there are two forms ofsoft lysine widely accepted in the marketplace: (1) lysine HCl, which isa crystalline and dried salt of lysine, and (2) liquid lysine, which isa concentrated solution of substantially pure lysine freebase in water.It is a generally accepted fact that lysine freebase is simpler tomanufacture (on a pure lysine basis) because the manufacture of salts oflysine such as lysine HCl requires several additional processing steps.However, these advantages are somewhat offset by additionaltransportation costs incurred in delivering liquid lysine. Additionallythe handing of lysine freebase requires an investment in additionalinfrastructure for the customer. Hence, in general lysine freebase isviable for only large volume customers.

The ability of a dried form of lysine freebase that is free flowing anddoes not exhibit significant caking properties is important aspect ofthe process for increasing the application of lysine freebase for smallvolume customers.

In one aspect a composition comprising a granule of a dried lysine saltadmixed with dried free lysine freebase wherein the lysine saltcomprises between 10 percent and 80 percent of the granule is described.In certain embodiments the composition may comprise a granule that has acore of a dried lysine freebase surrounded by a coating of a driedlysine salt.

In another aspect a composition comprising a granule having an innercore containing a first fraction of a dried lysine salt, a medial layercoating the core comprised of a dried lysine freebase, and an outerlayer coating the medial layer comprised of a second fraction of driedlysine salt is described. In certain embodiments, the composition maycomprise a granule of a dried threonine admixed with dried free lysinefreebase wherein the lysine freebase comprises between 10 percent and 80percent of the granule. In certain other embodiments the composition maycomprise a granule of a dried threonine admixed with dried lysine saltwherein the lysine salt comprises between 10 percent and 80 percent ofthe granule. In certain other embodiments a composition comprising agranule of a dried threonine admixed with dried lysine salt and driedfree lysine freebase wherein the lysine components, comprise between 10percent and 80 percent of the granule is described.

In another aspect a method is described where a fermentation is donewith a microorganism to produce a fermentation broth containing a cellmass and a soluble lysine fraction, followed by a method to separate thecell mass from the solubilized lysine fraction; followed by purifyingthe solubilized lysine fraction and neutralizing a portion of thesolubilized lysine fraction with a mineral acid to produce a lysinesalt. Certain embodiments may additionally include a method for sprayagglomerating the solubilized lysine fraction and lysine salt to produceheteromorphic lysine granules.

In another aspect a composition is described which comprises a granulethat has a core of a dried lysine salt surrounded by a coating of adried lysine freebase. In certain embodiments the composition may alsocomprise a granule that has a core of a dried lysine freebase surroundedby a coating of a dried threonine freebase. In certain other embodimentsthe composition may comprise a granule that has a core of a driedthreonine freebase surrounded by a coating of a dried lysine salt.

In other aspects are described compositions comprising dried lysinefreebase that absorbs less than 10% water when exposed to a temperatureof 10 degrees Celsius to 50 degrees Celsius and a humidity of between30% and 91% relative humidity for a period of 24 to 168 hours.

In certain embodiments lysine and salts of lysine may be produced by afermentation of Corynebacterium glutamicum. In certain other embodimentsthe threonine may be produced by Escherichia Coli fermentation.

In certain yet other aspects a method is described for the use of acomposition comprising granules of dried lysine freebase coated with alysine salt for at least one application selected from the groupconsisting of a fertilizer and an animal feed. Certain embodiments mayinclude a feed additive for ruminants, that consists essentially ofcores containing an acid salt of a basic amino acid, and effectiveamounts of a first coating layer and a second coating layer coatedsequentially on the surface of each core, wherein said first coatinglayer contains at least one first coating agent selected from the groupcomprising salts of a basic amino acid, freebase of an amino acid,alkali metal salt, nitrogen source, phosphate source, potassium source,and the second coating layer contains as a second coating agent selectedfrom the group comprising salts of a basic amino acid, freebase of anamino acid, alkali metal salt, nitrogen source, phosphate source,potassium source.

In certain embodiments the first coating agent may be at least one aminoacid selected from the group comprising methionine, leucine, isoleucineand tryptophan. In certain embodiments the second coating agent is atleast one amino acid selected from the group comprising methionine,leucine, isoleucine, valine, cysteine, tryptophan, threonine andphenylalanine. Other embodiments include a free-flowing powder of alysine freebase, having irregular nonspherical morphology coated with alayer of salt of lysine and a particle size distribution ranging from 10μm to 800 μm. Certain other embodiments include a free-flowing powder ofa salt of lysine, having irregular nonspherical morphology coated with alayer of lysine freebase and a particle size distribution ranging from10 μm to 800 μm. Certain yet other embodiments include a free-flowingpower of a lysine freebase, having multiphase morphology of roughlyspherical shape that comprises alternating layers of lysine freebase andlysine hydrochloride or threonine arranged concentrically, In certainembodiments a free-flowing power of a salt of lysine, having multiphasemorphology of roughly spherical shape that comprises alternating layersof lysine freebase and a salt of lysine or threonine arrangedconcentrically are described. Certain embodiments may includeheteromorphic granules of lysine or threonine that have a morphologyselected from core-shell, gradient, ice-cream cone, raspberry, salt andpepper or onion. In certain embodiments the granules may have more thanone type of morphologies. Certain yet other embodiments may includeheteromorphic granules of lysine or threonine that are additionallyco-coated with mineral salts. In certain embodiments, the salts mayprovide nitrogen, phosphorous and potassium nutrients to the granules.Additional embodiments describe heteromorphic granules that have anN—P—K ratio of 1:1:1. In some embodiments the N—P—K ratio may be 2-1-1,3-1-1, 3-2-1 or 2-3-1. Also described herein are processes for producingthe heteromorphic granules described herein.

Additional embodiments include producing the heteromorphic granules at afirst location, and transporting the composition to a second location.In certain other embodiments the first location and the second locationmay be countries.

Additional embodiments describe lysine granules that are produced by amicro-organism that is not genetically modified. Yet additionalembodiments include a facility operatively configured to perform theprocess or make the compositions described herein.

DETAILED DESCRIPTION

Definitions

Prior to describing the present invention in detail, certain terms thathave plain meanings generally understood by those of ordinary skill inthe art are nevertheless defined herein to better distinguish nuances inmeaning intended by the inventors. It is understood that the definitionsprovided herein are intended to encompass the ordinary meaningunderstood in the art without limitation, unless such a meaning would beincompatible with the definitions provided herein, in which case theprovided definitions control.

“About” when used with reference to a numerical expression, means thegreater of: (1) the degree of error of a typical instrument or processused to measure the items referenced by the expression, (2) plus orminus 10% of the stated value; or (3) with respect to a range, nearenough to the minima or maxima of the range so as not to have anynoticeable difference in form or function in comparison to an elementexactly at the stated minima or maxima.

“Dry” or “Dried” means a material has a moisture content of less than15% wt/wt, or has been treated to reduce the moisture content of thematerial to less than 50% the moisture content of the same material notso treated.

The term “lysine” means the amino acid lysine (C₆H₁₄N₂O₂) and salts orderivatives thereof, and includes all isomers of lysine (i.e., L-lysine,D-lysine, and any mixture of L- and D-lysine).

For convenience of expression, the term “dryer” will hereafter be usedto describe any suitable drying means such as a spray dryer, drum dryer,tunnel dryer, rotary dryer, tray dryer, and spray granulator.

The terms “spray granulation”, “spray granulation step”, and“agglomeration” will hereafter be regarded as equivalent terms.

The term “separation” when applied to a fermentation broth willhereafter be used to describe the separating of a lysine fermentationbroth into two fractions: a cell rich lysine broth and a substantiallycell free lysine broth. Any suitable separating means or combination ofseparating means may be used. Separation may be achieved by means offiltration (e.g. ultra- and microfiltration), and mechanical methodssuch as centrifugation, hydroclones, rotary vacuum filters, settlingtanks, depth filters and decanting.

The terms “evaporation” and “evaporated” will hereafter be used todescribe the removal of water by evaporation, which is carried out inthe approximate temperature range of between 140 degree F. and 214degree F., with a pressure between 2.9 psia and 11 psia (vacuum).

The terms “lysine hydrochloride” and “lysine HCL” will hereafter beregarded as equivalent terms.

The terms “lysine sulfate” and “lysine H₂SO₄” will hereafter be regardedas equivalent terms.

The term “lysine freebase” means the amino acid lysine in the absence ofa neutralizing salt.

The term “material containing lysine” will hereafter be used to describeany material of manufacture that contains any form of lysine alone or incombination with other materials and is commercially used at least inpart for delivery of lysine. Suitable forms of lysine in a materialcontaining lysine include, but are not limited to, a lysine fermentationbroth with or without cell mass, a dried lysine fermentation broth,lysine hydrochloride, lysine sulfate, and/or lysine freebase.

The term “final lysine feed supplement” will hereafter be used todescribe a commercially available material containing lysine f having alysine of a purity within a range between about 15% and 80% lysine,measured as a percent of lysine by weight of material, and which is usedto supplement feed for a non-human animal.

DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic of granulated lysine feed product comprisinglysine salt 20 core surrounded by lysine freebase 10 shell covered byanother shell of lysine salt 20.

FIG. 2 is a schematic of granulated lysine feed product comprisinglysine freebase 10 core surrounded by lysine hydrochloride 20 shellcovered by another shell of lysine freebase 10.

FIG. 3 is a schematic of granulated lysine feed product comprisinglysine salt 20 core surrounded by lysine freebase 10 shell.

FIG. 4 is a schematic of granulated lysine feed product comprisinglysine freebase 10 core surrounded by lysine salt 20 shell.

FIG. 5 is a schematic of granulated lysine feed product comprisinglysine freebase 10 core surrounded by lysine freebase 10 shell.

FIG. 6 is a schematic is a schematic of granulated lysine feed productcomprising threonine 40 core and lysine freebase 10 shell.

FIG. 7 is a schematic is of granulated lysine feed product comprisinglysine freebase 10 core and threonine 40 shell.

FIG. 8 is a schematic is of granulated lysine feed product comprisingthreonine 40 core and lysine hydrochloride 20 shell.

FIG. 9 is a schematic is of granulated lysine feed product comprisinglysine hydrochloride 20 core and threonine 40 shell.

FIG. 10 is a schematic is of granulated lysine feed product comprisingthreonine 40 core surrounded by a lysine hydrochloride 20 shell which inturn is also surrounded by another shell of lysine freebase 10.

FIG. 11 is a schematic is of granulated lysine feed product comprisinglysine hydrochloride 20 core surrounded by a threonine 40 shell which inturn is also surrounded by another shell of lysine 10 freebase.

FIG. 12 is a schematic is of granulated lysine feed product comprisinglysine freebase 10 core surrounded by a lysine hydrochloride 20 shellwhich in turn is also surrounded by another shell of threonine 40.

FIG. 13 is a schematic of granulated lysine feed products with differentpluralities of cores of lysine freebase 101 lysine hydrochloride 20 orthreonine 40 shells on cores of lysine freebase 10, lysine hydrochloride20 or threonine 40 or a plurality thereof.

FIG. 14 is a schematic of representative particle morphologies.

FIG. 15 is a flow chart, showing the principal steps in a process formaking an amino acid feed supplement in which a salt of an amino acid ismixed with a freebase amino acid to produce a substantially dust free,free flowing granular amino acid product.

FIG. 16 is a flow chart, showing the principal steps in a process formaking an amino acid feed supplement in which a salt of an amino acid ismixed with a freebase amino acid to produce a substantially dust free,free flowing granular amino acid product.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

One aspect of this teaching provides a free flowing dried amino acidproduct containing lysine that exhibits reduced caking properties incomparison to dried lysine freebase alone. Various embodiments focus ona heteromorphic lysine granule product with greater pourability overlysine freebase alone and higher lysine content than lysine saltproducts alone. In certain embodiments the granules are a combination oflysine freebase, and a salt of lysine, and/or with threonine or a saltof threonine. Other embodiments may include pure free dry freebaselysine or blends of lysine freebase and a salt of lysine such as lysinehydrochloride with a concentration of lysine freebase ranging from 10percent by weight to 100 percent by weight.

Pure dry lysine freebase may be used to make the granules. “Pure” inthis context means at least 90% of the dry weight of the material islysine freebase. As the proportion of lysine freebase is increased thecost savings associated with manufacturing the product are expected tobe higher. Blending of a salt of lysine is usually required to modifythe handling characteristics of the blend so that the final product iseasy to handle and package. One especially desired aspect is improvementin the flowability, pourability and anticaking properties of the blendsduring packaging, storing and handling.

In one aspect lysine granules of “onion morphology” or core-shellmorphology may be produced. Onion morphology may be a multiphasemorphology of roughly spherical shape that comprises alternating layersof different forms of lysine or threonine arranged concentrically,typically with all layers being of similar thickness. In an embodimentthe different forms of lysine may comprise lysine freebase, lysinehydrochloride, lysine sulfate or lysine cell broth. In anotherembodiment threonine or different forms of threonine may be used. In yetanother embodiment, various mineral salts that provide a nutritive valuein animal feed may also be used. Such salts may include a solidpotassium salt, such as potassium chloride, mixed with an ammoniumnitrate-containing liquid or solid salt phase that also containsammonium phosphate, or to which ammonium phosphate may also be added.

Various morphologies of lysine granules may be of the type shown innon-limiting embodiments depicted in FIGS. 1-12. For instance, asdepicted in FIG. 1, a roughly spherical shape morphology may comprise acore of lysine hydrochloride 20 surrounded by a shell of lysine freebase10 and a second shell of lysine hydrochloride 20. An alternativeembodiment, as depicted in FIG. 2, may be a roughly spherical shapecomprising a core of lysine freebase 10 surrounded by a shell of lysinehydrochloride 20 and a second shell of lysine freebase 10. The innercores may in certain embodiments, be about 400 microns in diameter. Incertain other embodiments the granules may be between 10 microns to 800microns. In another non-limiting embodiment, a core of lysine freebase10 may be surrounded by a shell of lysine hydrochloride 20 as depictedin FIG. 3, or a core of lysine hydrochloride 20 may be surrounded by ashell of lysine freebase 10 as depicted in FIG. 4.

One embodiment of the onion morphology may comprise a core of lysinefreebase 10 coated with a single outer layer (shell) of lysinehydrochloride 20 as depicted in FIG. 5, resulting in improved flowproperties.

Another aspect may comprise an heteromorphic lysine containing granulethat includes threonine. In one embodiment of this aspect, a core ofthreonine 40 is surrounded by a shell of lysine freebase 10 as depictedin FIG. 6. In another embodiment of this aspect, a core of lysinefreebase 10 may be surrounded by a shell of threonine 40 as depicted inFIG. 7. Another non-limiting embodiment may comprise a core of threonine40 surrounded by a shell of lysine hydrochloride 20 as depicted in FIG.8. Yet another non-limiting embodiment may comprise a core of lysinehydrochloride 20 surrounded by a shell of threonine 40 as depicted inFIG. 9.

Yet another aspect may comprise a core of threonine 40 surrounded by alayer of lysine hydrochloride 20 surrounded by a shell of lysinefreebase 10 as depicted in FIG. 10. In one particular embodiment, asdepicted in FIG. 11, the core may be lysine hydrochloride 20 surroundedby a layer of threonine 40 surrounded by shell of lysine freebase 10. Inanother embodiment, as depicted in FIG. 12, the core may be lysinefreebase 10, surrounded by a layer of lysine hydrochloride 20 surroundedby a shell of threonine 40.

In another aspect, lysine granules of a “raspberry morphology” or“cauliflower morphology” may be produced. In such case the granules thusobtained have a distorted or irregular morphology, which resembles thatof “raspberries” or of “Cauliflowers”, rather than spherical beads. Suchmorphologies of the final product may also in another embodiment, havean irregular nonspherical morphology and a particle size distributionranging from 10 μm to 800 μm.

In one embodiment, the raspberry morphology as depicted in FIG. 13Aincludes several cores of irregular granules of lysine hydrochloride 20surrounded by a shell of lysine freebase 10. In a particular embodimentas depicted in FIG. 13B, irregular granules of lysine freebase 10 may besurrounded by a shell of lysine hydrochloride 20.

In another embodiment, the raspberry morphology as depicted in FIG. 13Cincludes several cores of irregular granules of lysine freebase 10surrounded by a shell of threonine 40, or in an alternative embodimentshown in FIG. 13D, cores of irregular granules threonine 40 surroundedby a shell of lysine freebase 10.

A still further aspect of the present teaching is a compositioncomprising lysine freebase, lysine hydrochloride or threonine granulesprimarily of gradient morphology, that is, wherein the composition ofthe particles gradually changes from the center to the surface of thegranule.

A further aspect of the present teaching is a composition comprisinglysine freebase, lysine hydrochloride or threonine granules primarily ofinterpenetrating network morphology wherein there are two co-continuousor co-centric shells of two different compositions creating an entangle.

A still further aspect of the present teaching is a compositioncomprising lysine freebase, lysine hydrochloride or threonine granulesprimarily of “salt-and-pepper” morphology wherein the particles arecomposed of two or more different compositions that are in separatedomains.

Still another aspect of the present teaching is a composition comprisinglysine freebase, lysine hydrochloride or threonine granules primarily of“ice-cream cone” morphology wherein two or more particles of differentcompositions, share a surface of contact that may be large or small.

Other morphologies that the particles may possess are “lobed”morphology, interpolymer morphology or “hairy particles” comprisinglysine freebase, lysine hydrochloride or threonine granules.

A still further aspect of the present teaching is a compositioncomprising lysine freebase, lysine hydrochloride or threonine granulescontaining a combination of two or more morphologies mentioned above.Some of the morphologies discussed above are illustrated in FIG. 14.

The various embodiments of the onion or raspberry morphology describedherein are understood to be non-limiting and one of ordinary skill inthe art may tailor them suitably to obtain a desired flow behavior ofthe finished product.

Various non-limiting examples of lysine products suitable for use in thepresent disclosure include, but are not limited to, water soluble saltsof lysine, such as, for example, lysine monohydrochloride (“lysine(HCl)”), lysine hydrate, lysine dihydrochloride, and lysine sulfate,lysine freebase; aqueous solutions of lysine freebase; granular lysine;lysine fermentation cell waste; lysine fermentation cell mass; lysineraffinate; a lysine mother liquor, or mixtures of any thereof.

According to other non-limiting embodiments, an aqueous solution oflysine freebase may be used, which may comprise an aqueous solutioncomprising from about 45% by weight to about 55% by weight of lysinefreebase. In other non-limiting embodiments, the lysine content of theaqueous solution of lysine freebase may be increased as desired byeither removal or lowering the amount of water in the solution or by theaddition of an additional lysine product, such as a soluble salt oflysine, for example, lysine HCl and/or lysine sulfate. Alternatively,according to other non-limiting embodiments, the lysine content of theaqueous solution of lysine freebase may be decreased as desired by theaddition of water to the solution.

A method for preparing the heteromorphic granules described in thevarious embodiments of this disclosure is shown in the principle stepsof an inventive process in FIG. 15. The processes described herein maybe used to produce a lysine feed supplement with a final lysine purityin the range theoretically between about 35% and 80%. Fermentation 200may be carried out by any suitable means described in the art such asfor instance as describe in U.S. Pat. No. 6,017,555 the contents of inwhich, in their entirety are incorporated herein by reference.

After fermentation 200 a cell separation 21 may be used to separate thebiomass and obtain a substantially cell-free lysine broth 21B. The cellfree broth 21B is then processed through a chromatography step 22 toobtain a purified lysine freebase stream 22A. The lysine freebase is maythen be subjected to evaporation 23 to increase its dry solids andacidified using a mineral acid 25 in a crystallizer 30 to crystallizesalt of lysine, such as for example, lysine hydrochloride. The salt oflysine may then be dried in dryer 32.

The salt of lysine 28 may have a purity in a range between about 35% and80% lysine, measured as a percent of freebase per kg. The lysine brothfrom the cell separation step may also be, in one embodiment,agglomerated with the salt of lysine by using a spray granulator 61 toprovide particles of lysine in the core with particles of lysine orThreonine in the shell. The agglomerated particles, may also in oneembodiment, be sifted in sieve 62 to provide the final lysine feedsupplement 78. Oversized particles from sieve 62 may be processedthrough a grinder 68 and be used as “recharge” material for spraygranulator 61.

In an alternate embodiment of the inventive process shown in FIG. 15,the lysine freebase 40 used in the spray granulator 61 may be obtainedeither from cell separation step 21, chromatography 22 or evaporation23.

In another alternative embodiment of the inventive process shown in FIG.16, the broth from fermentation 200 may be subjected to evaporation 50.After evaporation to increase its dry solids, the product may beacidified 51 using a mineral acid 60. The acidified product may then bedried 52 using techniques known in the art such as, but not limited todrum drying, spray drying, vacuum tray drying, vacuum belt drying etc.to obtain salts of lysine 53 which may serve as raw material for spraygranulator 61.

In another embodiment threonine 29 (either freebase or a salt there of)may be added to the spray granulator 61 to obtain either a shell or acore containing the aforementioned amino acid.

In yet another embodiment threonine 29 may be replaced with any othersuitable amino acid either in freebase form, or a salt there of, such astryptophan, methionine etc.

In another embodiment sieve 62 and grinder 68 may be used to obtain anagglomerated product of the desired particle size.

In on aspect of this disclosure lysine freebase 400 may be obtained fromany one of streams 36, 37 or 38. In one embodiment of this disclosurelysine freebase 400 may be mixed with small quantities of acid such thatthe stream 400 may be a mixture of lysine freebase and a salt of lysine.

In one aspect of this disclosure commercially available liquid lysinemay be used as a base core in spray co-agglomeration with a lysine saltshell In one embodiment, the Liquid lysine™ brand lysine is anapproximately 50% (by weight) aqueous solution of lysine freebaseobtained by concentrating lysine from a lysine fermentation broth.

In another aspect lysine monohydrochloride (HCl) may be used as a basecore with a lysine freebase shell. lysine hydrochloride is commerciallyavailable in the form of lysine hydrochloride fromArcher-Daniels-Midland Company, Decatur, Ill. Lysine hydrochloride maybe obtained from, for example, but not limited to, purifying the productof a lysine fermentation process by crystallization of the hydrochloridesalt. lysine hydrochloride (available from Archer-Daniels-MidlandCompany, Decatur, Ill., as well as other suppliers) may be utilizedeither as a granular solid or as an aqueous solution.

While another aspect of this disclosure is the harvesting and processingof lysine base from fermentation broth, the composition and nature ofthe fermentation medium may vary. For example, any suitable high lysineproducing organism taken from the genus E.Coli Corynebacterium orBrevibacterium may be used to inoculate the fermentation medium. The pHis adjusted and maintained at approximately 7.2 with ammonium hydroxide.The temperature is maintained at about 32 degree. C. The feed is Glucoseand (NH₄)₂SO₄ with the glucose concentration initialized at about 10g/l.

The fermentation medium can be inoculated into the fermentation vesselby using standard microbiological practices which are known to thoseskilled in the microbiology art. The fermentation vessel should beequipped with a stirrer, a ventilation system, and a temperature controldevice to maintain the fermentation at about 30 degree C. to about 32degree C. The fermentation is carried out until the lysine baseconcentration is about 92 g/l (grams per liter) and the total dry solidsis about 218 g/l. Aseptic techniques should be observed throughout thefermentation process to avoid a contamination of the fermentation brothwith non-lysine producing organisms. The process produces a lysine feedsupplement in the form of a substantially dust free, free flowing,granular lysine from fermentation broth comprising a salt of lysineco-granulated with lysine freebase.

In another embodiment, the substantially cell free enriched lysine brothis atomized by a nozzle 56 to provide an atomized spray of substantiallycell free enriched lysine broth to make a percolating bed of lysineparticulates in a spray granulator 61. The lysine particulates have aparticle size of less than about 177 micron (i.e. particles that canpass through 80 mesh) and between the size range of about 100 micron and177 micron. The bed of the spray granulator may be a fluidized bed oflysine particulates and is operated at a temperature between about 30degrees C. and 100 degree C. The position of the nozzle 56 is adjusteduntil it is just above the fluidized bed of lysine particulates.Substantially cell free enriched lysine broth is sprayed onto thefluidized bed of lysine particulates to initiate the agglomerationprocess.

In an alternate embodiment a solution of lysine hydrochloride is sprayedonto the fluidized bed of lysine particulates to initiate theagglomeration process. In a yet another alternate embodiment a solutionof threonine is sprayed onto the fluidized bed of lysine particulates toinitiate the agglomeration process. In a further alternative embodimenta solution of tryptophan is sprayed onto the fluidized bed of lysineparticulates to initiate the agglomeration process. The agglomerationprocess is allowed to continue to produce the substantially dust free,free flowing, granular lysine coated with a shell of lysinehydrochloride or threonine or lysine freebase, in the size range betweenapproximately 177 micron and 1190 micron, or in the size range ofbetween about 177 micron to 420 micron. The product is then screened andsorted for size at sieve 62 Granules at 62 that are too large (e.g. inthe size range of greater than about 1190 micron) are ground in agrinder at 68 to a smaller particle size (e.g. in the size range of lessthan about 177 micron) and combined with material that is too small 84(e.g. in the size range of less than about 177 micron) to producerecycled lysine particulates (shown “recharge” on FIGS. 14 and 15) andreturned to the spray granulator 61 as a starting material which act asseeds for the agglomeration process. The substantially dust free, freeflowing, granular lysine product in the size range of about 177 micronto 1190 micron pass through the sieving process and are acceptable asthe end product at 78. However, a range is from about 177 micron to 420micron may be used which can pack better and reduces cost for shipment.

The lysine concentration in the lysine fermentation broth may be about90 g/l lysine to about 200 g/l lysine, measured as a percent of freebaseper kg. However, the lysine concentration can vary from one fermentationrun to the next. Hence, the use of a fermentation broth containing about90 g/l lysine means that other suitable concentrations of lysine in thefermentation broth are acceptable. However, the lysine concentration inthe fermentation broth should not be below about 30 g/l. Althoughultrafiltration is the one method for obtaining the substantially cellfree lysine broth in step 21 in FIG. 13, this does not mean othermethods can not be used. The cells could also be removed by mechanicalseparation techniques, such as centrifugation. Other suitable methodsinclude microfiltration and decanting.

This disclosure envisages the removal of cells from the lysinecontaining fermentation broth by various other processes. For example,the fermentation broth 20 could be split equally and about 50%centrifuged and the remaining 50% ultrafiltered with the outputs fromboth cell removal processes combined to produce a substantially cellfree lysine broth. This flexibility will enhance the practice of theinvention in an industrial setting. Although the present inventionenvisages the addition of material containing lysine to thesubstantially cell free concentrated lysine broth, the addition of suchmaterial to the concentrated lysine broth might be omitted altogether ifthe desired concentration of lysine (measured as freebase) is such thatthe addition is unnecessary. For example, the step of adding a materialcontaining lysine might be omitted if the concentration of lysine in thesubstantially cell free concentrated lysine broth substantially exceedsabout 35% lysine, measured as a percent of freebase per kg. If the cellfree concentrated lysine broth contains substantially more than about35% lysine, measured as a percent of freebase per kg, the lysine brothis a substantially cell free enriched lysine broth.

Experience has shown that there is a relationship between the orificesize of the nozzle 56, flow rate, and gauge pressure. While the nozzlesize may be 0.0615″, various other nozzles can also be used to supplythe spray. In particular, nozzle designs supplied by Spraying SystemsCo., PO Box 7900, Wheaton, Ill. 60189, USA work well to produce a finespray. The spray granulator can be purchased from Glatt Air Techniques,20 Spear Road, Ramsey, N.J. 07446-1288, USA.

Experience also suggests that manufacturing lysine granules on acommercial scale will require several nozzles to atomize and sprayenriched lysine broth onto a proportionally larger bed of percolatingparticles of lysine.

The percolating bed of particles should comprise lysine particles ofsufficiently small size to function as seeds for the agglomerationprocess. The lysine particulates may be less than about 177 micron insize and about 100 micron and 177 micron. In the agglomeration process,the seed particles simultaneously grow in size and are dried as they aresprayed with the enriched lysine permeate. The agglomeration process isaided by various components which are inherently present in the enrichedlysine broth, namely: lysine fermentation broth, lysine hydrochloride,lysine sulfate and water. Such components may act as binder and aredefined as substances which provide the sticky component to enable theseeds in the agglomeration process to build up in size.

The source of the lysine particulates used to produce and seed thefluidized bed of lysine in the spray granulator is not critical althoughthe source is either obtained from atomizing the substantially cell freeenriched lysine broth from step 53 in FIG. 15 or from recycled lysineparticulates (described as “recharge” in FIG. 15).

Alternatively, the fluidized bed of lysine particulates could beproduced by spray atomizing either a lysine containing fermentationbroth, a substantially cell free lysine broth, and substantially cellfree concentrated lysine broth or any mixture of these to produce a drypowder of lysine granules. Another example of a suitable source of thelysine particulates would be dry purified lysine hydrochloride powderand lysine sulfate which has been dried to a powder. The source oflysine particles may be sieved to remove lumps and sorted for particlesless than about 177 micron (The may be in the size range between about100 micron and 177 micron).

Experience has shown that the agglomeration process becomesself-sustaining by using the particles from recycling particles at 88 oneither a batch or semi-continuous basis.

lysine has a C to N ratio of 3:1 The lysine products according tovarious non-limiting embodiments may comprise nitrogen content rangingfrom about 9% N to about 20% N, depending of the formulation. In certainembodiments, the nitrogen content of the lysine products may range fromabout 9% N to about 15% N.

In another aspect of this disclosure, the products produced using theembodiments described herein, may be used to produce fertilizercompositions, such as, those described in co-pending applications U.S.Provisional Application Ser. No. 60/726,749, filed Oct. 14, 2005, andU.S. Provisional Application Ser. No. 60/789,051, filed Apr. 3, 2006,the disclosures of which are incorporated in their entirety by referenceherein.

In yet another additional non-limiting embodiment, mineral or mineralsalts may be coated on the granules described herein to provide N—P—Knutritional value to the granules for use as for instance but notlimited to animal feed, fertilizer, potting soil compositions, golfgreens and lawn fertilizers, horticultural and agricultural fertilizersand mulches. Other suitable mineral or mineral salts include thosecontaining zinc, manganese, magnesium, calcium or iron that may becombined alone or in combination with other minerals in theheteromorphic lysine granule.

In an additional non-limiting embodiment, the compositions describedherein, may be produced at a first geographic location and transportedor shipped to a second geographic location. For instance, a facility atthe first geographic location may be able to produce a product moreeconomically than a facility at the second location due to variousfactors. The factors may include, for example, lower costs of materials,lower costs of energy (e.g., electricity and/or natural gas or otherpetroleum products), lower costs of labor (e.g., wages paid toemployees), lower costs of environmental controls or effects, or anyother requirement for production of the compositions. Thus, the costs ofproducing the products in the first geographic location may be less thanthe costs of producing the products in the second geographic location,resulting in the production costs being less in the first geographiclocation.

In such an instance, the compositions may be produced at the firstgeographic location and shipped to the second geographic location suchas by transport over water with ships or barges, trucking, flying, byrail, or other means of transportation. The geographic location may be acounty, a state, a country, a continent, and/or combinations of anythereof. In this manner the product may be produced, for example, in afirst county, state, country, or continent, and transported to and/orsold in a second county, state, country, or continent.

The examples below are only representative of some aspects of thisdisclosure. It will be understood by those skilled in the art thatprocesses as set forth in the specification can be practiced with avariety of alterations with the benefit of the disclosure. Theseexamples and the procedures used therein should not be interpreted aslimiting this disclosure in any way not explicitly stated in the claims.

EXAMPLE 1

In this embodiment manufacturing processes for heteromorphic lysinegranules are described.

Three different process intermediate from the lysine manufacturingprocess described in FIGS. 15-16 are utilized as raw materials.

(a) Liquid lysine solutions with a nominal lysine concentration of 50%(Stream “A”) but with an allowable range of 20% -80% solids.

(b) lysine hydrochloride solution that is used to feed the lysinehydrochloride crystallization step as described in FIG. 1 (Stream “B”).

(c) Dry lysine hydrochloride final product (Stream “C”)

The various feed streams (A, B, or C) may be used to produce an aminoacid product as follows:

(1) Starting with a sample from the Stream “A”, the product is dried toproduce a liquid lysine powder with the desired moisture content.

(2) Starting with a sample from the Stream “A”, the product isevaporated to raise the dry solids concentration and dried to obtain afree flowing lysine powder.

(3) Sample of Streams “A” and “B” is blended and dried to a desiredmoisture level.

(4) Sample of Streams “A” and “B” is blended and evaporated to a highersolids concentration. The evaporated product is dried to obtain a freeflowing lysine powder

(5) The product from tests 1 and 2 is spray coated with lysinehydrochloride using a spray agglomerator type dryer.

(6) The product from Stream “C” is spray coated with Stream “A” using aspray agglomerator type dryer.

(7) The products from tests 1-6, either by them selves or in combinationis dry blended with Stream “C”.

(8) The product of Stream “A” is pH adjusted to a target of 2.0-12.0 anddried to the desired moisture content.

(9) The product of Stream “A” is pH adjusted to a target of 2.0-12.0 andevaporated to raise the dry solids and dried to obtain a free flowinglysine powder.

EXAMPLE 2

RUN 2: In this Embodiment Coating on Lysine HCl of Lysine Freebase wasStudied.

A solution of 90 parts by volume of 725 g/l lysine freebase containing70 percent dry solids was co-sprayed a solution of 10 parts by volume oflysine mother liquor (35 from FIG. 15) containing 50.8 percent drysolids and 320.4 g/l lysine freebase on a lysine HCL recharge using aspray granulator. An initial recharge of 250 g product was used. Theinlet dryer temperature was kept at 275° F. and bed temperature wasbetween 180° to 185° F. Feed was preheated to a temperature of 160° F.ad the dryer was sprayed at rates to keep the outlet temp greater than159° F. Spray agglomeration was initially started at 8 ml/min for first15 minutes and gradually increased to 20 ml/min as outlet temperaturespermitted. A total of 1800 ml of lysine freebase and 900 ml of lysineHCL were used. Spray agglomeration was continued until the weight of thebed reached 1.5 kg where in product was recovered, sieved and analyzed.Results are presented in Tables 1-3.

EXAMPLE 3

RUN 3: In this Embodiment Effect of Coating Lysine and ThreonineFreebase on Lysine Salts was Studied.

A solution of 60 parts by volume of 725 g/l lysine freebase containing70 percent dry solids was co-sprayed a solution of 40 parts by volume ofthreonine ultrafiltration concentrate blend containing 70 percent drysolids and 120 g/l threonine freebase on a lysine HCL recharge using aspray granulator. An initial recharge of 250 g product was used. Theinlet dryer temperature was kept at 70° C. and bed temperature wasbetween 150-170 degrees F. Feed was preheated to a temperature of 100°F. ad the dryer was sprayed at rates to keep the outlet temp greaterthan 159° F. Spray agglomeration was initially started at 8 ml/min forfirst 15 minutes and gradually increased to 15 ml/min as outlettemperatures permitted. Spray agglomeration was continued until theweight of the bed reached 1.5 kg wherein product was recovered, sievedand analyzed. Results are presented in Tables 1-3.

EXAMPLE 4

RUN 4: In this Embodiment Effect of Coating Lysine Freebase on LysineSalts was Studied.

A solution of 80 parts by volume of 725 g/l lysine freebase containing70 percent dry solids was co-sprayed a solution of 20 parts by volume oflysine freebase ultrafiltration concentrate blend containing 50 percentdry solids and 250 g/l lysine freebase on a lysine HCL recharge using aspray granulator. An initial recharge of 800 g product was used. Theinlet dryer temperature was kept at 148 C and bed temperature wasbetween 150-170 degrees F. Feed was preheated to a temperature of 71 Cad the dryer was sprayed at rates to keep the outlet temp greater than148 C. Spray agglomeration was initially started at 8 ml/min for first15 minutes and gradually increased to 15 ml/min as outlet temperaturespermitted. A total volume of 2000 ml feed was sprayed. Sprayagglomeration was continued until the weight of the bed reached 1.3 kgwhere in product was recovered, sieved and analyzed. Results arepresented in Tables 1-3.

EXAMPLE 5

RUN 5: In this Embodiment Effect of Coating Lysine Freebase and LysineUF Concentrate on Lysine Salts was Studied.

A solution of 50 parts by volume of 725 g/l lysine freebase containing70 percent dry solids was co-sprayed a solution of 50 parts by volume oflysine freebase ultrafiltration concentrate blend containing 50 percentdry solids and 250 g/l lysine freebase on a lysine HCL recharge using aspray granulator. An initial recharge of 800 g product was used. Theinlet dryer temperature was kept at 148 C and bed temperature wasbetween 150-170 degrees F. Feed was preheated to a temperature of 71 Cad the dryer was sprayed at rates to keep the outlet temp greater than148 C. Spray agglomeration was initially started at 8 ml/min for first15 minutes and gradually increased to 15 ml/min as outlet temperaturespermitted. A total volume of 2000 ml feed was sprayed. Sprayagglomeration was continued until the weight of the bed reached 1.3 kgwhere in product was recovered, sieved and analyzed. Results arepresented in Tables 1-3.

EXAMPLE 6

RUN 6: In this Embodiment Effect of Coating Lysine Freebase and LysineMother Liquor on Lysine Salts was Studied.

A solution of 91 parts by volume of 725 g/l lysine freebase containing70 percent dry solids was co-sprayed a solution of 9 parts by volume oflysine freebase mother liquor containing 48.3 percent dry solids and320.4 g/l lysine freebase on a lysine HCL recharge using a spraygranulator. An initial recharge of 400 g product was used. The inletdryer temperature was kept at 148 C and bed temperature was between150-170 degrees F. Feed was preheated to a temperature of 71 C ad thedryer was sprayed at rates to keep the outlet temp greater than 148 C.Spray agglomeration was initially started at 8 ml/min for first 15minutes and gradually increased to 15 ml/min as outlet temperaturespermitted. A total volume of 1850 ml feed was sprayed. Sprayagglomeration was continued until the weight of the bed reached 1.915 kgwhere in product was recovered, sieved and analyzed. Results arepresented in Tables 1-3.

EXAMPLE 7

RUN 7: In this Embodiment Effect of Coating Lysine Freebase and LysineMother Liquor on Lysine Salts was Studied.

A solution of 90 parts by volume of 725 g/l lysine freebase containing70 percent dry solids was co-sprayed a solution of 10 parts by volume oflysine freebase mother liquor containing 44 percent dry solids and 320.4g/l lysine freebase on a lysine HCL recharge using a spray granulator.An initial recharge of 400 g product was used. The inlet dryertemperature was kept at 70 C and bed temperature was between 140-160degrees C. Feed was preheated to a temperature of 37.7 C ad the dryerwas sprayed at rates to keep the outlet temp greater than 70 C. Sprayagglomeration was initially started at 8 ml/min for first 15 minutes andgradually increased to 15 ml/min as outlet temperatures permitted. Atotal volume of 1800 ml feed was sprayed. Spray agglomeration wascontinued until the weight of the bed reached 1.915 kg where in productwas recovered, sieved and analyzed. Results are presented in Tables 1-3.

EXAMPLE 8

RUN 6: In this Embodiment Effect of Coating Lysine Freebase and LysineMother Liquor on Lysine Salts was Studied.

A solution of 91 parts by volume of 725 g/l lysine freebase containing70 percent dry solids was co-sprayed a solution of 1 part by volume oflysine freebase mother liquor containing 48.3 percent dry solids and320.4 g/l lysine freebase on a lysine HCL recharge using a spraygranulator. An initial recharge of 400 g product was used. The inletdryer temperature was kept at 148 C and bed temperature was between140-170 degrees C. Feed was preheated to a temperature of 71 C ad thedryer was sprayed at rates to keep the outlet temp greater than 148 C.Spray agglomeration was initially started at 8 ml/min for first 15minutes and gradually increased to 15 ml/min as outlet temperaturespermitted. A total volume of 1850 ml feed was sprayed. Sprayagglomeration was continued until the weight of the bed reached 1.915 kgwhere in product was recovered, sieved and analyzed. Results arepresented in Tables 1-3.

TABLE 1 Run Number 2 3 6 7 8 70% Free 60/40 (V/V) 4 5 91/9(V/V)90/10(V/V) 91/9(V/V) base L-Lysine 80/20(V/V) 50/50(V/V) Free base Freebase Free base Lysine Threonine Lysinefree Free base Lysine LysineLysine and w/Lysine UF base and Lysine and and lysine and lysine lysineHCL final concentrate Lysine UF lysine UF mother mother mother FeedSource coat blend concentrate concentrate liquor liquor liquor Feed A1800 ml 70% DS 70% DS 70% DS 70% DS 70% DS 70% TS of Lysine LysineLysine Lysine Lysine Lysine 70% DS freebase freebase freebase freebasefreebase freebase Lysine containing containing containing containingcontaining containing free base 725 g/l 725 g/l 725 g/l 725 g/l 725 g/l725 g/l Lysine Lysine Lysine Lysine Lysine Lysine Feed B No other 70% TS50% UF 50% TS UF 48 3% DS 44% DS 48 3% DS feed Threonine ~240-260 g/l~240-260 g/l Lysine Lysine Lysine free mixture ~120-150 g/l free basefree base base containing 320 g/l Lysine Final Coat 900 mls N/A N/A N/AN/A N/A N/A of HCL lysine. Run conditions Inlet 70 C. 70 C. 148 C. 148C. 148 C. 70 C. Unavailable temperature Out 65-70 C. 65-70 C. 148 C. 148C 148 C 70 C. Unavailable temperature Feed 37.7 C. 37.7 C. 71 C. 71.1 C.71 C. 37.7 C. Unavailable temperature Feed rate 20 ml/min. 8-15 ml/min.8-15 ml/min. 8-15 ml/min. 8-15 ml/min. 8-15 ml/min. 8-15 ml/min.Recharge .250 kg .800 kg .800 kg .400 kg. Lysine .400 kg. Weight HCLRecharge Lysine Lysine HCL Lysine HCL Lysine HCL Lysine 1800 ml LysineHCL Source HCL HCL total spray Feed totals 1800 mls 1600 ml 2000 ml 2000ml 1850 ml 1800 ml 1850 ml L-lysine total spray total spray total spraytotal total spray total spray w/900 mls spray HCL coating Final 1.500 kg1 400 kg 1.3 kg 1.300 kg 1.915 kg ~1 800 kg 1.915 kg Weight

TABLE 2 Feed Analysis Run Number 2 3 4 5 6 7 8 pH of Feed 9.2 9.8 ~9.0-10.0  ~9.0-10.0 9.8 9.8 9.8 TS 70.0% TS 60 ~60-70 ~60-71 ~60-72~60-73 ~60-74 G/L Lysine N/A 491 ~725 g/l ~725 g/l ~725 g/l ~725 g/l~725 g/l +/− +/− +/− +/− +/−    50 g/l    50 g/l    50 g/l    50 g/l   50 g/l

TABLE 3 Product Analysis Run Number 2 3 4 5 6 7 8 Bulk 30.8 36 28.00%36.3 23.3 32.3 23.3 Density +16 mesh 0.00% 3.00% 4.00% 1.40% Unavailable1.00% Unavailable +40 mesh 21.60% 58.60% 26.90% 40.90% Unavailable36.20% Unavailable +80 mesh 72.20% 38.10% 69.80% 52.50% Unavailable65.30% Unavailable +Pan 7.1% 3.7 3 5.5 Unavailable 2 UnavailableMoisture 0.50% 1.20% 2.10% 1.30% 2.20% 1.50% 2.20% Purity by 96.80%97.40% 89.20% 92.30% 98.50% 97.50% 98.50% HPLC Purity by 103.40% 91.70%99.50% 101.90% 104.80% 107.90% 104.80% Titration

EXAMPLE 9

In this embodiment caking tests on lysine granules prepared according tothe various embodiments of this disclosure are performed.

A sample of 10.0 grams of product prepared according to variousembodiments of this disclosure is stored in a glass vial and is exposedto various relative humidity conditions for 7 days before evacuation.Upon evacuation the products are examined visually a relative scale:

0=Flowed Easily, no clumps.

1=Needed a gentle tap to initiate flow.

2=Needed a sharp tap to initiate flow.

3=Solid cake.

4=Laden with water.

The caking tests are performed under the following conditions.

A. Relative humidity 33%, Temperature 30 degrees C.

B. Relative humidity 51%, Temperature 30 degrees C.

C. Relative humidity 63%, Temperature 30 degrees C.

D. Relative humidity 72.8%, Temperature 30 degrees C.

E. Relative humidity 84%, Temperature 30 degrees C.

F. Relative humidity 91%, Temperature 30 degrees C.

The granules prepared according to the various aspects of thisdisclosure are found to rate 0 or 1 on the relative scale indicatinggood flowability.

Specific methods and compositions described herein are representative ofpreferred embodiments and are exemplary and not intended as limitationson the scope of the invention. Other objects, aspects, and embodimentswill occur to those skilled in the art upon consideration of thisspecification, and are encompassed within the spirit of the invention asdefined by the scope of the claims. Where examples are given, thedescription shall be construed to include but not to be limited to onlythose examples. It will be readily apparent to one skilled in the artthat varying substitutions and modifications may be made to theinvention disclosed herein without departing from the scope and spiritof the invention, and from the description of the inventions, includingthose illustratively set forth herein, it is manifest that variousmodifications and equivalents can be used to implement the concepts ofthe present invention without departing from its scope. A person ofordinary skill in the art will recognize that changes can be made inform and detail without departing from the spirit and the scope of theinvention. The described embodiments are to be considered in allrespects as illustrative and not restrictive. Thus, for example,additional embodiments are within the scope of the disclosure and withinthe following claims.

1. A heteromorphic granule comprising lysine free base and a lysine salt2. The heteromorphic granule of claim 1 wherein the lysine salt isselected from the group consisting of lysine hydrochloride and lysinesulfate.
 3. The heteromorphic granule of claim 1 wherein the granule hasa core of the dried lysine freebase surrounded by a coating of a driedlysine salt.
 4. The heteromorphic granule of claim 1 wherein the granuleis comprised of a dried lysine salt admixed with dried free lysine basewherein the lysine salt comprises between 10 percent and 80 percent ofthe granule.
 5. The heteromorphic granule of claim 1 wherein the granulehas an inner core containing a first fraction of a dried lysine salt, amedial layer coating the core comprised of a dried lysine freebase, andan outer layer coating the medial layer comprised of a second fractionof dried lysine salt.
 6. The heteromorphic granule of claim 1 whereinthe granule has a core of a dried lysine salt surrounded by a coating ofa dried lysine freebase.
 7. A heteromorphic granule comprising driedthreonine admixed with dried lysine wherein the lysine comprises between10 percent and 80 percent of the granule.
 8. The heteromorphic granuleof claim 7 wherein the lysine comprises a lysine salt.
 9. Theheteromorphic granule of claim 7 wherein the lysine is comprised oflysine freebase
 10. The heteromorphic granule of claim 7 wherein thelysine is comprised of dried lysine salt and dried free lysine base. 11.The heteromorphic granule of claim 7 wherein the granule has a core of adried lysine freebase surrounded by a coating of the dried threonine.12. The heteromorphic granule of claim 7 wherein the granule has a coreof the dried threonine surrounded by a coating of a dried lysine saltadmixed with dried lysine freebase.
 13. A heteromorphic granulecomprising at least two components, at least one of which is driedlysine freebase at 10-80% the weight of the granule, and wherein thegranule absorbs less than 10% water when exposed to a temperature of 10degrees Celsius to 50 degrees Celsius and a humidity of between 30% and91% relative humidity for a period of 24 to 168 hours.
 14. Thecomposition of any one of claims 1-13 wherein the granule furtherincludes at least one inorganic compound comprising at least one elementselected from the group consisting of nitrogen, phosphorous, potassium,magnesium, manganese, iron and zinc.
 15. A method comprising: fermentinga microorganism to produce a fermentation broth containing a cell massand a soluble lysine fraction; separating the cell mass from thesolubilized lysine freebase fraction; purifying the solubilized lysinefraction to obtain a lysine enriched fraction; neutralizing a portion ofthe lysine enriched fraction with a mineral acid to produce a lysinesalt; spray agglomerating at least one of the solubilized lysinefreebase fraction and the lysine enriched fraction with the lysine saltto produce heteromorphic lysine granules.
 16. The method of claim 15wherein the lysine salt is dried before being spray agglomerated with atleast one of the solubilized lysine freebase fraction and the lysineenriched fraction.
 17. The method of claim 15 wherein the lysine salt isa solubilized lysine salt fraction which is spray agglomerated with atleast one of the solubilized lysine freebase fraction and the lysineenriched fraction.
 18. The method of claim 15 wherein the lysine salt isselected from the group consisting of lysine hydrochloride and lysinesulfate.
 19. The method of claim 15 further including adding a nutritivemineral or mineral salt to the spray agglomeration.
 20. A method of useof a composition comprising the heteromorphic granules according to anyone of claims 1-14 for at least one application selected from the groupconsisting of a fertilizer and an animal feed.
 21. A feed additive forruminants, which consists essentially of cores containing an acid saltof a basic amino acid, and a first coating layer and a second coatinglayer coated sequentially on the surface of each core, wherein saidfirst coating layer contains at least one first coating agent selectedfrom the group comprising salts of a basic amino acid, freebase of anamino acid, alkali metal salt, nitrogen source, phosphate source,potassium source, and the second coating layer contains as a secondcoating agent selected from the group comprising salts of a basic aminoacid, freebase of an amino acid, alkali metal salt, nitrogen source,phosphate source, potassium source.
 22. The feed additive according toclaim 21, wherein the first coating agent is at least one amino acidselected from the group comprising methionine, leucine, isoleucine andtryptophan.
 23. The feed additive according to claim 21, wherein thesecond coating agent is at least one amino acid selected from the groupcomprising methionine, leucine, isoleucine, valine, cysteine,tryptophan, threonine and phenylalanine.
 24. The heteromorphic granuleof any one of claims 1-14 wherein the granule has an irregularnon-spherical morphology and a particle size distribution ranging from10 μm to 800 μm and wherein a powder consisting of the heteromorphicgranules is characterized as free flowing when exposed to a temperatureof 10 degrees Celsius to 50 degrees Celsius and a humidity of between30% and 91% relative humidity for a period of 24 to 168 hours.
 25. Theheteromorphic granule of any one of claims 1-14 having multiphasemorphology of roughly spherical shape that comprises alternating layersof lysine freebase and at least one of lysine hydrochloride andthreonine arranged concentrically.
 26. A powder comprising theheteromorphic granule of any one of claims 1-14 wherein the granules inthe powder have a morphology selected from the group consisting of: acore-shell morphology, a gradient morphology, an “ice-cream cone”morphology, a “raspberry” morphology and a “salt-and-pepper” morphology.27. A fertilizer composition, which consists essentially of corescontaining an acid salt of a basic amino acid, and effective amounts ofa first coating layer and a second coating layer coated sequentially onthe surface of each core, wherein said first coating layer contains atleast one first coating agent selected from the group comprising saltsof a basic amino acid, freebase of an amino acid, alkali metal salt,nitrogen source, phosphate source, potassium source, and the secondcoating layer contains as a second coating agent selected from the groupcomprising salts of a basic amino acid, freebase of an amino acid,alkali metal salt, nitrogen source, phosphate source, potassium source.28. The fertilizer composition according to claim 27, wherein the firstcoating agent is at least one amino acid selected from the groupcomprising methionine, leucine, isoleucine and tryptophan.
 29. Thefertilizer composition according to 27, wherein the second coating agentis at least one amino acid selected from the group comprisingmethionine, leucine, isoleucine, valine, cysteine, tryptophan, threonineand phenylalanine.
 30. The fertilizer composition according to claim 27additionally including potassium, phosphorous, calcium, magnesium, orsodium mineral salt.
 31. The fertilizer composition according claim 27wherein the N—P—K ratio is selected from the group comprising 1-1-1,2-1-1, 3-1-1, 3-2-1 or 2-3-1.